Dioxazine coloring matters and process for preparing the same



Patented Aug. 8, 1944 DIOXAZINE COLORING MATTERS AND PROCESS FOR- PREPARING THE SAME- Frithjof Zwilgmeyer, Wilmington, Del., assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application February 20, 1943,

Serial No. 476,647

8 Claims.

This invention relates to novel dioxazine coloring matters. More particularly,this invention deals with novel compounds of the dioxazine series, characterized by the presence of sulfonamide radicals in the structural formula. It is an object of this invention to provide novel coloring matters of the dioxazine series. Another obiect is to provide dioxazine dyestuffs of superior affinity 'to various fibers and of increased solubility in various solvents, thereby permitting the utilization of this type of color in many applications heretofore impossible. A still further object is the preparation of new blue dioxazine dyestuffs of very'desirable shade, which have good solubility, exhaust, strength, and excellent fastness properties. Other and further important objects of this invention will appear as the description proceeds.

Now; according to this invention, I have found that dioxazine coloring matters having the desirable properties above indicated may be obtained by introducing sulfonamide radicals into the molecule of the color. More particularly, I introduce the sulfonamide radical into the aryl radical of the arylamine which is condensed with the central quinone nucleus and ring-closed to form the two oxazine rings. The nitrogen atom of the sulfonamide radicals may be substituted by hydrogen or various organic radicals, and the aryl nucleus containing the sulfonamide radical may possess in addition various auxochromic or chromophoric substituents, such as halogen, hydroxy, amino, alkoxy, etc. In addition, the entire molecule may carry sulfonic acid groups.

Accordingly, the novel compounds of this invention may be characterized by the general formula:

Y-S 02 (I) X! wherein X and X individually represent a substituent from the group consisting of hydrogen, halogen and alkyl; Y represents an amine radical, such as NH, NHR, or

R and B being any organic radicals whatsoever; Z is a substituent from the group consisting of hydrogen, halogen, hydroxy, amino, OR, NHR,

R and R being any organic radicals whatsoever; in other words, Z is a substituent from the group consisting of hydrogen, halogen, hydroxy, amino, substituted hydroxy and substituted amino; finally, :1: is a numeral which may have a value anywhere from zero to 4. p

The properties of the dioxazine compound may to some extent be controlled by proper choice of the substituents Y and Z in the above formula. For instance, if either of these is an organic radical having sulfo or carboxy groups, the product will have increased water-solubility. By choosing Y or Z so as to possess ethanol, methanol or glycolether radicals, the resulting dioxazine compound maybe endowed with solubility in alcohol. Afilnity for cotton may be increased by choosing an amino benzazole radical," for instance the radical of a fi -amino-benzamidazolone, for Y or Z. 011 the other hand, aryl radicals having primary amino groups (NHz), tend to give improved affinity for W001. The synthesis of my novel series of compounds may be efiectedaccording to my preferred mode of procedure, by starting with a halogen-nitrobenzene-sulfonyl chloride having at least one position freeortho to the N02 group, and converting the sulfonyl chloride radical into a sulfonamide radical by reaction with ammonia or with any. desirable ammonia-substitution derivative. The nuclear halogen atom may likewise be exchanged for'any suitable organic radicals by steps of procedure which are per se well known. The resulting nitrobenzene sulfonamide compound of general formula Z OzN SOz-Y wherein X, X, Y and Z have the same significance as above.

This intermediate is then ring-closed in standard manner, for instance by treatment with oleum, chlorosulfonic acid or concentrated sulfuric acid.

The last mentioned treatment for ring-closure is generally accompanied by sulfonation, and in the subsequent treatment of the product some desulfonation or shifting of the SO3H groups takes place, as a result of which the exact number of the SOsH groups and their positions are uncertain. It is believed, however, that a: in the above formula (I) is in any event not greater than 4.

In some cases, the ring-closure step may be followed by a special after-treatment step with anhydrous HCl (r NaCl+anhydrous H2804) at elevated temperature, as more fully illustrated in Example 1 below. I find that this step enhances the exhausting properties of the final dyestufi, and give altogether greater tinctorial strength and washing fastness.

The following examples will further illustrate my preferred mode of operation, without however limiting this invention to the details set forth. Parts mentioned are by weight.

EXAMPLE 1 PART APREPARATION OF THE INTERMEDIATE .rial No. 393,483, Patent No. 2,336,664) by heating an aqueous solution of the two intermediates,

made slightly alkaline to Brilliant Yellow with soda ash, in a sealed vessel in the presence of parts of magnesium oxide for 24 hours, at tem- .peratures varying from 130 to 142 C. The reaction mixture is made alkaline with caustic soda and filtere'd. The filtrate is neutralized with hydrochloric acid and the separated nitro-diary lamine compound of the formula OzN is filtered off and washed with water.

The last named nitro body is now subjected to reduction by heating at the boil with 80 parts of iron, 10 parts of concentrated hydrochloric acid and 300 parts of water. The mass is now made alkaline to Clayton Yellow by the aid of sodium hydroxide, filtered, and the filtrate is acidified with acetic acid to precipitate the amino body. The latter is then filtered ofif, washed free of acid and dried.

PART B-PREPARATION or THE DYESTUFF 60 parts of the amino-diaryl-amine resulting from Part A are condensed, with 20 parts of tetrachloro-benzoquinone (chloranil), by refluxing a mixture of the two in alcohol, in the presence of 14 parts of anhydrous sodium acetate or 15 parts of sodium bicarbonate, for 16 hours. The reaction product is filtered hot and the cake is washed with 50 parts of hot alcohol and then dried. 70 parts of a dark condensation product are thus obtained.

5 parts of the above dark condensation product are now added slowly to 100 partsv of fuming sulfuric acid, containing 20% sulfuric anhydride, at 23-25 C. and kept there for three hours, whereupon the temperature is raised to C. and kept there for one hour. The reaction mixture is added to ice and the formed dyestufi is filtered off and washed with an aqueous sodium chloride solution until the cake is free of any mineral acidity. The wet filter cake is slurried in water, neutralized with soda ash, salted out, and filtered. After drying, the dye is obtained in good yield as a purple product. It dyes animal and vegetable fibers in bright blue tints of good light fastness.

If a redder shade of blue is desired, the following alternate methods may be used: Instead of raising the temperature to 45 C. as in the preceding paragraph, the reaction mixture may be diluted with sulfuric acid to obtain finally a monohydrate solution; or, the dye may first be isolated, dried and then added to monohydrate. In the former case the addition of some sodium chloride is preferable. In both cases, the reaction mixture is kept at 50-100 C. for about one hour, drowned in ice and isolated in the abovedescribed manner. Noticeably redder shades of blue are obtained by this treatment at higher temperature. Similar redder shades of blueare obtained by substituting 30% oleum for the 20% oleum in the above samples. The yields are, in all cases, about'the same.

A similar dye is obtained by using chlorosulfonic acid instead of the oleum in the above example. This dye may be redissolved in monohydrate at temperatures from 65 to C., as in the above example, and isolated in the same manner, resulting in similar shade improvements.

XAMPLE 2 B of Example 1, are added to 100 parts of sulfuric acid monohydrate; the reaction mixture is heated to 150 C., held there for one-half hour, and isolated as a sodium salt as in Example 1. The dye is obtainedin goodyieldas a dark powder. It dyes animal and vegetable fibers bluish-gray tints of good light fastness.

EXAMPLE 3" 7 Example 1 is repeated, except that the tetrachloro-benzoquinone in Part B is replaced by the,

molecular equivalent of toluquinone. The dye is obtained in good yield as a dark purple powder. It dyes animal and vegetable fibers bluish-gray tints of good light fastness.

EXAMPLE 4 Example 1 is repeated, except that the tetrachloro-benzoquinone is replaced by the equivalent Weight of benzoquinone. The dye is' obtained in good yield as a dark powder. It dyes animal and vegetable fibers bluish-gray tints of,

good light f astness.

EXAMPLE 5 Example 1 is repeated, except that the tetrachloro-benzoquinone is replaced by theequivalent weight of 2:5-dichloro-benzoquinone. The dye is obtained in good yield as a' dark powder. It dyes animal and vegetable fibers bright blue tints of good light fastness.

EXAMPLE 6 Example 1 is repeated, except that thetetrachloro-benzoquinone is replaced by the equivalent weight of tetrabromo-benzoquinone. The dye is obtained in good yield as a dark powder. It dyes animal and vegetable fibers blue tints of good light fastness. M It will be understood that the above examples are merely illustrative and that numerous variations in the details thereof may be practiced without departing from the spirit of this invention. For instance, instead of using chloro-benzoquinones or toluquinones, longer-chain alkylated benzoquinones may be employed. Likewise, instead of the amino-diaryl amine specified in Example 1 for condensation with the quinone, other aryl amines of the general formula SOzY may be employed, wherein Y and Z may signify substituents as defined in the introductory parts of this specification. Typical additional illus- .trations of such intermediates synthesized by me,

and the shades of the resulting dioxazinedyestufi's upon cotton are given in Tables A and B, below.

In all cases of Table A, I have started with 4 nitro 1 chlorobenzene-2-sulfony1- chloride; condensed same with an ammonia derivatives,

g H 'Table A '[Zfi5 ainino2beniimidazdlbne; Y===variable1 I I Formula of ammonia A j derivativez; 7

meme derivative R Shade employed to dioxazine dye furnish radical Y HN 1 Ammonia NHa I a Reddisbblue. 2 D1methylamine HN(CH2)| Do.

3 Sulfanili'c acid HQNOSOaHW Greenish-blue.

I 4 2,5-dichloro- HzNQ Do.

aniline.

I Cl I 5 2,5-dich1oro- HQNGCHSQ; Do.

p-toluidine. I

O1 v I 6 2,4,5-trichloro- HzN C1 Do aniline.

7 5-amino-2-ben- HzN NH Dark blue.

zimidazolone. I

NH-CO 8 N-ethyl-alpha- CzH5NH Do.

naphthylamine In Table B, I have started likewise in all cases vJith 4-nitro-1-chlorobenzene-2-sulfonyl chloride; condensed same first with monoethanol amine according to Example 1; condensed the product further with an ammonia derivative of formula as given in the table; reduced N02 group in resulting l-substituted 4 nitrobenzene-Z-beta-hydroxy-ethylamino-sulfone; condensed 2 moles of resulting amine with 1 mole of chloranil, and finally ring-closed by aid of oleum according to Example 1 above. The dioxazine dyestufi thus obtained was dyed uponcotton.

Table B [Y=monoethanol-amine; Z=variable1 Formula of ammonia derivative: Ammonia derivative R Shade of employed to furnish dioxazine dye radical Z upon cotton 1 Ammonim; NH! Reddish-blue. 2 Ethanolamine HzN-CzH4OH Do. 3 Hexamethylene- HzN(CH2)o-NH, Do.

diannne. 4 N,N-d1methyl-hexa- HzN(CHz)sN(OHa)z Do.

methylene-diamine.

s Aniline ENG Blue.

In a similar manner other sulfonamide containing arylamines may be synthesized for condensation with chloranil or similar quinone to give eventually novel dioxazine dyestuffs which, besides showing in most cases extraordinary good cotton affinity and excellent light fastness, may also be of interest for other fibers, since it is possible to select the groups connected to the sulfone radical or to the aryl radical so as to obtain good afiinity on specific fibers and to render the dyes soluble in solvents in which ordinary dioxazine compounds are only sparingly soluble or not soluble at all. Additional typical illustrations of. such intermediates and their preferred mode of synthesis are given in Tables C and D below.

Table C [Z=Cl, Y=variable1 All compounds in this table may be prepared by condensing 4-nitro-1-chlorobenzene-2-sulfonyl-ohloride with an ammonia derivative as indicated, and then reducing the nitro group.

,. Ammonia Arylamine-sulfonamide intermediate derivative used to furnish radical Y- 1 Cl 'Ammonla.

OzNHz 2 NH Dimethylamine.

S OrN CH3) 2 Monoethanol 3.5 3 TQ amine.

OrNH-CzH4OH NH2QC1 Aniline. '40 sol-N 5 NH 0 C1 2,5dichloroaniline.

SOr-NH 45 5-amino-2-benzimi- 6 O dazolone.

iOTNH H so NH-C O 5 amino 2 -methyl 7 Q C1 benzimidazole.

s oi-Nnil ir I NH-CCH:

Table 1) :31, on or 0on3; Y=varlable1 1 NH Condense initial material with gnilgfl, then with gmmontia; an eyer an re uce 111 ro SOrNH-G group.

Condense initial material with 2 'Q dimethyl amine, then with ammonia; Sandmeyer with S Oz-N 0 Hz) a KCN and reduce nitro group Like above, but condense with aniline and then with ammonia.

Oondense initial material with 4 NH OCHa aniline asnddthen with all};

M01113. 8.11 meyer 0-- SOz-NHO compo'und; methylate, and

reduce nitro group;

In the preceding examples and tables, the arylamine intermediate selected for condensation with the central quinone (formula IV above) had both its positions ortho to the NHz group free (that is, substituted only by hydrogen). In some cases it is permissible to start with arylarnine-intermediates in which one of the positions ortho to the NI-Iz group is occupied; this is especially true when the substituent in the ortho position is of a nature as to be eliminated during the ring-closure step in the form of alcohol (OCHs, OC2H5 group, etc.).

EXAMPLE 7 2-amino-anisolei-sulfone-dimethylamide (described in U. S. P. 1,678,599) was condensed with chloranil (in molar ratio 2:1) and ring-closed with sulfuric acid monohydrate at C. according to the procedure set forth in Example 2 above. The resulting dioxazine dyestufi dyed cotton a reddish brown shade.

The ring closure in this case presumably is attended by the limination of alcohol, according to the following scheme:

Similar results are obtained if the l-sulfone- 3. A dioxazine dyestuff of the formula dimethylamide compound above is replaced by O] s OzNHCiH4OH 02B) J any other intermediate of the general formula wherein the group Inc-o v R s ot-Y represents an amine radical from the group conh Y h e an of th values indicated sisting of unsubstituted, monosubstituted and X i i g g g sg y e disubstituted amine radicals, while :1: stands for It will be clear that my invention opens the ral not greater than 4. gate to a large series of new dioxazine colors in A dloxazme dyes/Buff of the formula which numerous dyestufis of desirable shade and excellent light fastness may be produced by Q 01 Y-SO: N o judicious selection of the initial components for condensation.

I claim as my invention: 1. Dioxazine dyestuffs of the general formula Q/ 0 N SOTY S 03H): YSOI 2|: Z h Qd t th d11f5 2 w erein esigna es e ra ca 0 -amino- /N\ benzimidazolone, Y is an amine radical from the I group consisting of unsubstituted, monosubstituted and disubstituted amine radicals, while S :0 stands for a numeral not greater than 4. X1 -(SO3H)== 5. A dioxazine dyestufi as in claim 4, wherein J Y stands for the radical, NH-C2H4OH, of monowherein X and X individually represent a subethanol-amine. stituent from the group consisting of hydrogen, 6. A dioxazine dyestufi as in claim 4, wherein halogen and alkyl; Y represents an amine radi- 40 Y stands for the radical, NH-C6H4-SO3H, of cal; Z represents a substituent selected from the sulfanilic acid. group consisting of hydrogen, halogen, hydroxyl, 7. The dioxazine dyestufi of formula 01 HOC2H4NHS o, N o NH- n U O Q s OPNH-GiHiOH S OaH): 01 l amino, substituted hydroxy and substituted wherein :1: is a numeral not greater than 4. amino; while a: is a numeral not greater than 4. 8. The process of producing a dioxazine dye- 2. Dioxazine dyestuffs of the general formula stllfi' which comprises condensing a benzo- R quinone with two molar proportions of a sub- Y O2S ititutzd aniliie having at leatslt one ortho posi- N O 1011 ree an con aining in e nuc eus suli fonamide substituent of the formula S82-Y, R V I I whereiighY ist an amine radical; and reacting upon e in ermediate quinone-diamine thus \N /\O I N/\ s ()2 Y formed with an agent of the group consisting of R/ X soarm sulfuric acid, oleum and chlorosulfonic acid,

whereby to close the rings adjacent to the quiwherein X and X individually represent a subnone nuc1eus stituent from the group consisting of hydrogen, halogen and alkyl; Y represents an amine radical; the group FRITHJ OF ZWEGMEYER.

represents an amine radical from the group consisting of unsubstituted, monosubstituted and disubstituted amine radicals, while :0 stands for a numeral not greater than 4.

CERTIFICATE OF CORRECTION.

Patent No. 2,555,1p97. I August 8, 191m.

FRITHJOF ZWILGMEYER.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 5, first column, line 68, for the word "produce" read -product; line 69, for "LL-"8115.110" read --5-a mino--; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the ease in the Patent Office.

Signed and sealed this 26th day of September, A. D. 19%.

Leslie Frazer (Seal) Acting Commissioner of Patents. 

